• The Bulletin of The Korean Astronomical Society
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• v.35 no.1
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• pp.30.2-30.2
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• 2010

Numerous operational anomalies and satellite failures have been reported since the beginnings of the "space age". Space weather effects on modern spacecraft systems have been emphasized more and more as increasing their complexity and capability. Energetic particles potentially can destroy and degrade electronic components in satellites. We analyzed the geostationary (GEO) satellite anomalies during 1997-2009 to search possible influences of space weather on the satellite anomalies like power problem, control processor problem, attitude control problem, etc. For this we use particle data from GOES and LANL satellites to investigate space weather effects on the GEO satellites' anomalies depending on Kp index, local time, seasonal variation, and high-energy electron contribution. As results, we obtained following results: (1) there is a good correlation between geomagnetic index(Kp) and anomaly occurrences of the GEO satellite; (2) especially during the solar minimum, occurrence of the satellite anomalies are related to electron flux increase due to high speed solar wind; (3) satellite anomalies occurred more preferentially in the midnight and dawn sector than noon and dusk sector; (4) and the anomalies occurred twice more in Spring and Fall than Summer and Winter; (5) the electron with the lowest energy channel (50-75keV) has the highest correlation (cc=0.758) with the anomalies. High association between the anomalies and the low energy electrons could be understand by the facts that electron fluxes in the spring and fall are stronger than those in the summer and winter, and low-energy electron flux is more concentrated in the dawn sector where the GEO satellite anomalies occurred more frequently than high-energy electron flux. While we could not identify what cause such local time dependences, our results shows that low-energy electrons (~100keV) could be main source of the satellite anomaly, which should be carefully taken into account of operating satellites.

• Bulletin of the Korean Chemical Society
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• v.31 no.1
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• pp.75-81
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• 2010

The reaction of N,N-diethyl carbamates of 1H-[1,2,3]triazolo[4,5-b]pyridin-1-ol (4-HOAt) 7, 3H-[1,2,3]triazolo[4,5-b]pyridin-3-ol (7-HOAt) 8, 1H-benzo[d][1,2,3]triazol-1-ol (HOBt) 9, 6-chloro-1H-benzo[d][1,2,3]triazol-1-ol (Cl-HOBt) 10, 6-(trifluoromethyl)-1H-benzo[d][1,2,3]triazol-1-ol ($CF_3$-HOBt) 11, and 6-nitro-1H-benzo[d][1,2,3]triazol-1-ol ($NO_2$-HOBt) 12 with morpholine and piperidine in $CH_3CN$ underwent acyl nucleophilic substitution to give the corresponding carboxamide derivatives. The reactants and products were identified by elemental analysis, IR and NMR. We measured the kinetics of these reactions spectrophotometrically in $CH_3CN$ at a range of temperatures. The rates of morpholinolysis and piperidinolysis were found to fit the Hammett equation and correlated with $\sigma$-Hammett values. The values were 1.44 - 1.21 for morpholinolysis and 1.95 - 1.72 for piperidinolysis depending on the temperature. The $Br{\phi}$nsted-type plot was linear with a $\beta_lg = -0.49 \pm 0.02$ and $-0.67 \pm 0.03$. The kinetic data and structure-reactivity relationships indicate that the reaction of 9-12 with amines proceeds by a concerted mechanism. The deviation from linearity of the correlation ${\Delta}H^#$ vs. ${\Delta}S^#$ and plot of $logk_{pip}$ vs. $logk_{morph}$ and $Br{\phi}$nsted-type correlation indicate that the reactions of amines with carbamates 7 and 8 is attributed to the electronic nature of their leaving groups.

• Bulletin of the Korean Chemical Society
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• v.30 no.10
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• pp.2393-2397
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• 2009

Second-order rate constants ($k_{HOO}$‒) have been measured spectrophotometrically for nucleophilic substitution reactions of Y-substituted phenyl benzenesulfonates (1a-g) with $HOO^-$ ion in $H_2O$ at $25.0\;{\pm}\;0.1\;{^{\circ}C}$. The Br$\phi$nsted-type plot is linear with ${\beta}_{lg}$ = ‒0.73. The Hammett plot correlated with with ${\sigma}^-$ constants results in much better linearity than ${\sigma}^o$ constants, indicating that expulsion of the leaving group occurs in the rate-determining step (RDS) either in a stepwise mechanism or in a concerted pathway. However, a stepwise mechanism in which departure of the leaving group occurs in the RDS has been excluded since $HOO^-$ ion is more basic and a poorer leaving group than the leaving Y-substituted phenoxide ions. Thus, the reactions of 1a-g with $HOO^-$ ion have been concluded to proceed through a concerted mechanism. The $\alpha$-nucleophile $HOO^-$ ion is more reactive than its reference nucleophile $OH^-$ ion although the former is ca. 4 p$K_a$ units less basic than the latter (i.e., the $\alpha$-effect). TS stabilization through intramolecular H-bonding interaction has been suggested to be irresponsible for the $\alpha$-effect shown by $HOO^-$ ion, since the magnitude of the $\alpha$-effect is independent of the electronic nature of substituent Y in the leaving group. GS destabilization through desolvation of $HOO^-$ ion has been concluded to be responsible for the $\alpha$-effect found in the this study.

• Bulletin of the Korean Chemical Society
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• v.30 no.10
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• pp.2371-2376
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• 2009

Three phenoxazine-based conjugated polymers, namely, the aryl substituted phenoxazine homopolymer (P1) as well as the dimeric phenoxazine-fluorene (P2) and phenoxazine-bithiophene (P3) copolymers, were synthesized via the Ni(0) mediated Yamamoto reaction and the palladium-catalyzed Suzuki coupling reaction. The weight-averaged molecular weights ($M_w$) of P1, P2, and P3 were found to be 27,000, 22,000, and 15,000, respectively, and their polydispersity indices were 3.6, 1.8, and 2.1. All the polymers were soluble in common organic solvents such as chloroform, toluene, and so on. The UV-visible absorption maxima for P1, P2, and P3 in the film state were located at 421, 415 and 426 nm, respectively, and the ionization potentials of the polymers ranged between 4.90 and 5.12 eV. All the studied phenoxazine-based polymers exhibited amorphous behavior, as confirmed by X-ray diffraction (XRD) and atomic force microscopy (AFM) studies. Thin film transistors were fabricated using the top-contact geometry. P1 showed much better thin-film-transistor performance than P2 or P3: A thin film of P1 gave a saturation mobility of 0.81 ${\times}\;10^{-3}\;cm^2V^{-1}s^{-1}$ and an on/off ratio of about $10^2$.

• Bulletin of the Korean Chemical Society
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• v.35 no.1
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• pp.177-181
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• 2014

Pseudo-first-order rate constants ($k_{obsd}$) have been measured spectrophotometrically for the reactions of Y-substituted-phenyl benzoates (5a-j) with potassium ethoxide (EtOK) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plots of $k_{obsd}$ vs. [EtOK] curve upward regardless of the electronic nature of the substituent Y in the leaving group. Dissection of $k_{obsd}$ into the second-order rate constants for the reactions with the dissociated $EtO^-$ and ion-paired EtOK (i.e., $k_{EtO^-}$ and $k_{EtOK}$, respectively) has revealed that the ion-paired EtOK is more reactive than the dissociated $EtO^-$. The Br${\phi}$nsted-type plots for the reactions with the dissociated $EtO^-$ and ion-paired EtOK exhibit highly scattered points with ${\beta}_{lg}$ = -$0.5{\pm}0.1$. The Hammett plots correlated with ${\sigma}^o$ constants result in excellent linear correlations, indicating that no negative charge develops on the O atom of the leaving Y-substituted-phenoxide ion in transition state. Thus, it has been concluded that the reactions with the dissociated $EtO^-$ and ion-paired EtOK proceed through a stepwise mechanism, in which departure of the leaving group occurs after the RDS, and that $K^+$ ion catalyzes the reactions by increasing the electrophilicity of the reaction center through a four-membered cyclic TS structure.

• Bulletin of the Korean Chemical Society
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• v.29 no.4
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• pp.799-804
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• 2008

An amphiphilic diacetylene compound was deposited on the surface of nano sized magnetite particles ($Fe_3O_4$) using a self-assembly method. The diacetylene molecular assembly formed on the surface of nanoparticle was subjected to photopolymerization. This resulted in the formation of a polymeric assembly on the surface of the nanoparticles in which the adjacent diacetylene molecules were connected through conjugated covalent networks. The presence of immobilized polymer species on the surface of nanoparticles is expected to protect them from agglomeration and ripening, thereby stabilizing their physical properties. In this work, $Fe_3O_4$ nanoparticles were prepared by chemical coprecipitation method and the diacetylene molecule 10,12- pentacosadiynoic acid (PCDA) was anchored to the surface of $Fe_3O_4$ nanoparticles through its carboxylate head group. Irradiation of UV light on the nanoparticles containing immobilized diacetylenes resulted in the formation of a polymeric assembly. Presence of diacetylene molecules on the surface of nanoparticles was confirmed by X-ray photoelectron spectroscopy and FT-IR measurements. Photopolymerization of the diacetylene assembly was detected by UV-Visible spectroscopy. Magnetic properties of the nanoparticles coated with polymeric assembly were investigated with SQUID and magnetic hysteresis showed superparamagnetic behaviors. The results put forward a simple and effective method for achieving polymer coating on the surface of magnetic nanoparticle.

• Bulletin of the Korean Chemical Society
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• v.35 no.2
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• pp.436-440
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• 2014

The ${\alpha}$-Effect; Ground state; Transition state; Intramolecular H-bonding; Yukawa-Tsuno plot; Second-order rate constants for aminolysis of 2-chloro-4-nitrophenyl X-substituted-benzoates (1a-h) have been measured spectrophotometrically in 80 mol % $H_2O/20$ mol % DMSO at $25.0^{\circ}C$. The Br${\emptyset}$nsted-type plot for the reactions of 2-chloro-4-nitrophenyl benzoate (1d) with a series of primary amines curves downward, which has been taken as evidence for a stepwise mechanism with a change in rate-determining step (RDS). The Hammett plots for the reactions of 1a-h with hydrazine and glycylglycine are nonlinear while the Yukawa-Tsuno plots exhibit excellent linearity with ${\rho}_X=1.22-1.35$ and ${\gamma}= 0.57-0.59$, indicating that the nonlinear Hammett plots are not due to a change in RDS but are caused by stabilization of substrates possessing an electron-donating group (EDG) through resonance interactions between the EDG and C=O bond of the substrates. The ${\alpha}$-effect exhibited by hydrazine increases as the substituent X changes from a strong EDG to a strong electron-withdrawing group (EWG). It has been concluded that destabilization of hydrazine through the electronic repulsion between the adjacent nonbonding electrons is not solely responsible for the substituent dependent ${\alpha}$-effect but stabilization of the transition state is also a plausible origin of the ${\alpha}$-effect.

• Bulletin of the Korean Chemical Society
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• v.35 no.2
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• pp.494-500
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• 2014

Indium-doped zinc oxide nanocrystals (IZO NCs), capped with stearic acid (SA) of different sizes, were synthesized using a hot injection method in a noncoordinating solvent 1-octadecene (ODE). The ligand exchange process was employed to modify the surface of IZO NCs by replacing the longer-chain ligand of stearic acid with the shorter-chain ligand of butylamine (BA). It should be noted that the ligand-exchange percentage was observed to be 75%. The change of particle size, morphology, and crystal structures were obtained using a field emission scanning electron microscope (FE-SEM) and X-ray diffraction pattern results. In our study, the 5 nm and 10 nm IZO NCs capped with stearic acid (SA-IZO) were ligand-exchanged with butylamine (BA), and were then spin-coated on a thermal oxide ($SiO_2$) gate insulator to fabricate a thin film transistor (TFT) device. The films were then annealed at various temperatures: $350^{\circ}C$, $400^{\circ}C$, $500^{\circ}C$, and $600^{\circ}C$. All samples showed semiconducting behavior and exhibited n-channel TFT. Curing temperature dependent on mobility was observed. Interestingly, mobility decreases with the increasing size of NCs from 5 to 10 nm. Miller-Abrahams hopping formalism was employed to explain the hopping mechanism insight our IZO NC films. By focusing on the effect of size, different curing temperatures, electron coupling, tunneling rate, and inter-NC separation, we found that the decrease in electron mobility for larger NCs was due to smaller electronic coupling.

• Bulletin of the Korean Chemical Society
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• v.34 no.4
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• pp.1115-1119
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• 2013

A kinetic study is reported for nucleophilic substitution reactions of benzyl 2-pyridyl thionocarbonate (5b) and t-butyl 2-pyridyl thionocarbonate (6b) with a series of alicyclic secondary amines in $H_2O$ at $25.0^{\circ}C$. General-base catalysis, which has often been reported to occur for aminolysis of esters possessing a C=S electrophilic center, is absent for the reactions of 5b and 6b. The Br${\o}$nsted-type plots for the reactions of 5b and 6b are linear with ${\beta}_{nuc}$ = 0.29 and 0.43, respectively, indicating that the reactions of 5b proceed through a stepwise mechanism with formation of a zwitterionic tetrahedral intermediate ($T^{\pm}$) being the rate-determining step while those of 6b proceed through a concerted mechanism. The reactivity of 5b and 6b is similar to that of their oxygen analogues (i.e., benzyl 2-pyridyl carbonate 5a and t-butyl 2-pyridyl carbonate 6a, respectively), indicating that the effect of modification of the electrophilic center from C=O to C=S (i.e., from 5a to 5b and from 6a to 6b) on reactivity is insignificant. In contrast, 6b is much less reactive than 5b, indicating that the replacement of the $PhCH_2$ in 5b by the t-Bu in 6b results in a significant decrease in reactivity as well as a change in the reaction mechanism (i.e., from a stepwise mechanism to a concerted pathway). It has been concluded that the contrasting reactivity and reaction mechanism for the reactions of 5b and 6b are not due to the electronic effects of $PhCH_2$ and t-Bu but are caused by the large steric hindrance exerted by the bulky t-Bu in 6b.

• Bulletin of the Korean Chemical Society
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• v.34 no.10
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• pp.2877-2882
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• 2013

Second-order rate constants ($k_{Ox^-}$) have been measured spectrophotometrically for nucleophilic substitution reactions of 4-nitrophenyl X-substituted-cinnamates (7a-7e) and Y-substituted-phenyl cinnamates (8a-8e) with butane-2,3-dione monoximate ($Ox^-$) in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The Hammett plot for the reactions of 7a-7e consists of two intersecting straight lines while the Yukawa-Tsuno plot exhibits an excellent linearity with ${\rho}_X$=0.85 and r=0.58, indicating that the nonlinear Hammett plot is not due to a change in the rate-determining step but is caused by resonance stabilization of the ground state (GS) of the substrate possessing an electron-donating group (EDG). The Br${\o}$nsted-type plot for the reactions of Y-substituted-phenyl cinnamates (8a-8e) is linear with ${\beta}_{lg}$ = -0.64, which is typical of reactions reported previously to proceed through a concerted mechanism. The ${\alpha}$-nucleophile ($Ox^-$) is more reactive than the reference normal-nucleophile ($4-ClPhO^-$). The magnitude of the ${\alpha}$-effect (i.e., the $k_{Ox^-}/k_{4-ClPhO^-}$ ratio) is independent of the electronic nature of the substituent X in the nonleaving group but increases linearly as the substituent Y in the leaving group becomes a weaker electron-withdrawing group (EWG). It has been concluded that the difference in solvation energy between $Ox^-$ and $4-ClPhO^-$ (i.e., GS effect) is not solely responsible for the ${\alpha}$-effect but stabilization of transition state (TS) through a cyclic TS structure contributes also to the Y-dependent ${\alpha}$-effect trend (i.e., TS effect).